CN107431185A - The manufacture method of lithium ion battery electrode, lithium ion battery and lithium ion battery electrode - Google Patents

The manufacture method of lithium ion battery electrode, lithium ion battery and lithium ion battery electrode Download PDF

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Publication number
CN107431185A
CN107431185A CN201680018564.5A CN201680018564A CN107431185A CN 107431185 A CN107431185 A CN 107431185A CN 201680018564 A CN201680018564 A CN 201680018564A CN 107431185 A CN107431185 A CN 107431185A
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lithium ion
ion battery
electrode
active material
interarea
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CN107431185B (en
Inventor
水野雄介
进藤康裕
中岛勇辅
川北健
川北健一
草地雄树
大泽康彦
佐藤�
佐藤一
赤间弘
堀江英明
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Secondary Cells (AREA)

Abstract

Even if in the case of being thickened it is an object of the invention to provide a kind of thickness of electrode, also good lithium ion battery electrode, lithium ion battery of the invention are included electronic conductivity with electrode：The 1st interarea for being arranged at the barrier film side of lithium ion battery and the 2nd interarea for being arranged at current collection side, it is characterised in that the thickness of above-mentioned electrode is 50~5000 μm；Between above-mentioned 1st interarea and above-mentioned 2nd interarea, containing average fiber length be 50nm less than 100 μm chopped fiber (A), average fiber length be more than 100 μm and be less than 1000 μm long fibre (B) and active material particle (C)；Above-mentioned chopped fiber (A) and above-mentioned long fibre (B) are conducting fibre.

Description

The system of lithium ion battery electrode, lithium ion battery and lithium ion battery electrode Make method
Technical field
The present invention relates to the manufacturer of a kind of lithium ion battery electrode, lithium ion battery and lithium ion battery electrode Method.
Background technology
In recent years, for environmental protection, highly desirable reduction carbon dioxide output.In automobile industry, expect to concentrate In the reduction of carbon dioxide output caused by the importing as electric automobile (EV) or mixed power electric car (HEV), because This, the exploitation of motor driving secondary cell deeply carrying out these practicality, getting a grip on.As secondary cell, energy Enough reach high-energy-density, the lithium rechargeable battery of high-output power density receives much concern.
In lithium rechargeable battery, negative or positive electrode active material etc. is typically respectively coated on positive pole using binding agent and used Or negative pole collector, form electrode.In addition, in the case of bipolar cell, pair with anode layer and negative electrode layer is formed Polar form electrode, positive active material etc. is coated with a surface of collector by using binding agent for the anode layer and shape Into；Negative electrode layer is coated with negative electrode active material etc. on the surface of opposite side by using binding agent and formed (for example, referring to patent Document 1).
In patent document 1, with 25 μm or so of thickness coating electrode formation paste, still, as raising battery The method of energy density, it is known to the method for improving the ratio of the positive electrode and negative material in battery.In patent document 2 Disclose, by thickening the thickness of electrode, reduce the relative scale of collector or barrier film, improve the side of the energy density of battery Method.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-86480 publications
Patent document 2：Japanese Unexamined Patent Publication 9-204936 publications
The content of the invention
The technical problems to be solved by the invention
As described in patent document 2, it is believed that if the thickness of electrode can be thickened, can reduce collector or every The relative scale of film is effective to the high capacity of battery.
But in bipolar electrode, if thickening the thickness of electrode, the active material remote apart from the distance of collector Ratio increase.Herein, it is believed that because the electronic conductivity of active material itself is not high, therefore from the active matter remote apart from collector The electronics movement of matter to collector can not be smoothed out.Therefore, only the thickness of electrode is thickened, even if the amount of active material increases Add, electronic conductivity is also deteriorated, and participates in the effective active matter ratio of the discharge and recharge in whole active materials and reduces.In addition, will When the thickness of electrode thickens, the ion diffusional resistance generated in electrode gap is big, and the charge/discharge capacity under high current is speed The problem of rate characteristic is greatly lowered.
Further, since the electronic conductivity of active material itself is not high, therefore attempt to add the second as conductive auxiliary agent The particulate matters such as acetylene black improve the method for electronic conductivity.But for the conductive auxiliary agent in particle shape, the thickness of electrode When thickening, it is difficult to play the effect for improving electronic conductivity.
For solving the technical scheme of technical problem
The present inventor in order to solve the above-mentioned technical problem and further investigate result find, using by chopped fiber, Both fibroplastic conducting fibres of long fibre, the conductive path that the thickness direction of shape paired electrode is electrically connected, make Obtain and can be moved from electronics caused by active material by conductive path to collector, now, by the way that fibre length is applied in combination Different chopped fibers and long fibre, when the thickness of electrode is thickened, the ionic conduction in electronic conductivity and space Property it is good, it is big to form effective active matter ratio, and the electrode that the speed characteristic under high current is improved, so as to complete this hair It is bright.
When the different chopped fiber of fibre length and long fibre is applied in combination, thus it is speculated that obtain the reasons why power output improves effect As described below.
(1) first, when using long fibre, it is believed that space between active material is shaped as more straight line, passes through the space The diffusion path length of lithium ion shorten.Therefore, ion diffusional resistance diminishes.
(2) when being further combined using chopped fiber, for " the active material-activity that can not be contacted using only long fibre Between material " and " between active material-long fibre ", more conductive paths can be formed.Therefore, resistance diminishes.
(1) and (2) result, both ion diffusional resistance and electronic resistance diminish.Therefore, carry out under high current Also a large amount of electricity can be exported during discharge and recharge, speed characteristic is improved.
That is, the present invention relates to a kind of lithium ion battery electrode, it includes：It is configured at the of the barrier film side of lithium ion battery 1 interarea, and the 2nd interarea on current collection side is configured at, wherein, the thickness of the electrode is 50~5000 μm, in the described 1st master Between face and the 2nd interarea, comprising：Average fiber length is 50nm less than 100 μm of chopped fiber (A), average fibre Tie up length be more than 100 μm and be less than 1000 μm long fibre (B), and active material particle (C), the chopped fiber (A) And the long fibre (B) is conducting fibre.The invention further relates to a kind of lithium ion battery, wherein, by the present invention lithium from Sub- electrode for cell is used for negative pole and/or positive pole.The invention further relates to a kind of manufacture method of lithium ion battery electrode, it is The manufacture method of the lithium ion battery electrode of the present invention, it includes：Process (Q1), the chopped fiber (A), the length will be included The slurry (Y) of fiber (B) and the active material particle (C) is coated on film (E)；And process (Q2), pressurizeed or Decompression, makes the active material particle (C), the chopped fiber (A) and the long fibre (B) be fixed on the film (E).This Invention further relates to a kind of manufacture method of lithium ion battery electrode, and it is the manufacturer of the lithium ion battery electrode of the present invention Method, it is characterised in that its spy includes：Process (T1), the chopped fiber (A), the long fibre (B) and the activity will be included Slurry (Y) coating of material particle (C) on the current collector, forms pulp layer on the current collector；And process (T2), barrier film is carried It is placed on the pulp layer, imbibition is carried out from the upper surface side of barrier film, so that the active material particle (C), the short fibre Dimension (A) and the long fibre (B) are fixed between the collector and the barrier film.
The effect of invention
The lithium ion battery electrode of the present invention, between the 1st interarea of electrode and the 2nd interarea, using by chopped fiber, length Both fibroplastic conducting fibres of fiber, the conductive path that the thickness direction of shape paired electrode is electrically connected, therefore, Collector can be flowed to by conductive path from electronics caused by active material.Therefore, even in by the thickness of electrode thicken for It is 50~5000 μm, suitable from electronics caused by the active material remote apart from collector relatively in the case of the amount of increase active material Sharply to reaching collector.Therefore, it is good to form electronic conductivity, and the lithium-ion electric of the high capacity suitable for lithium ion battery Pond electrode.
Brief description of the drawings
Fig. 1 is to represent that the lithium ion battery with the present invention is used as positive pole and the knot of the lithium ion battery of negative pole by the use of electrode The schematic cross-section of the example of structure.
Fig. 2 is the schematic cross-section for the positive pole for only representing the lithium ion battery shown in Fig. 1.
Fig. 3 (a) and Fig. 3 (b) is to represent to make chopped fiber and long fibre and active material particle is fixed on work on film The process schematic diagram of sequence.
Fig. 4 (a), Fig. 4 (b) and Fig. 4 (c) are to represent active material particle, chopped fiber and long fibre being fixed on collection The process schematic diagram of process between electric body and barrier film.
Description of reference numerals
1 lithium ion battery
10th, 210 lithium ion batteries are with electrode (positive pole)
11st, the 1st interarea of 211 positive poles
12nd, the 2nd interarea of 212 positive poles
13A chopped fibers
13B long fibres
14 positive active material particles
15th, 25 covering
16th, 26 conductive auxiliary agent
20th, 220 lithium ion batteries are with electrode (negative pole)
21st, the 1st interarea of 221 negative poles
22nd, the 2nd interarea of 222 negative poles
24 negative electrode active material particles
30 barrier films
40th, 50 collector
225 pulp layers
470 filter paper
Embodiment
Hereinafter, the present invention is described in detail.
The lithium ion battery of the present invention is included with electrode：It is arranged at the 1st interarea, the Yi Jishe of the barrier film side of lithium ion battery It is placed in the 2nd interarea on current collection side, it is characterised in that the thickness of above-mentioned electrode is 50~5000 μm；Above-mentioned 1st interarea with it is upper Between stating the 2nd interarea, contain：Average fiber length is chopped fiber (A), average fiber lengths of the 50nm less than 100 μm For more than 100 μm and be less than 1000 μm long fibre (B) and active material particle (C) and above-mentioned chopped fiber (A), on It is conducting fibre to state long fibre (B).
In the lithium ion battery electrode of the present invention, between the 1st interarea and the 2nd interarea, comprising：Average fiber length For 50nm less than 100 μm chopped fiber (A), average fiber length is more than 100 μm and is less than 1000 μm long fine Tie up (B) and active material particle (C).
Chopped fiber (A) and long fibre (B) are conducting fibre.
Fig. 1 is to represent that the lithium ion battery with the present invention is used as positive pole and the knot of the lithium ion battery of negative pole by the use of electrode The schematic cross-section of the example of structure.
Lithium ion battery 1 shown in Fig. 1 includes positive pole 10 and negative pole 20, be provided between positive pole 10 and negative pole 20 every Film 30.
The surface opposite with barrier film 30 of positive pole 10 is provided with collector 40, in the table opposite with barrier film 30 of negative pole 20 Face is provided with collector 50.Said structure is summarized, according to collector 40- positive pole 10- barrier film 30- negative pole 20- collectors 50 successively Form laminated construction, generally lithium ion battery 1.
The lithium ion battery of the present invention is free from the concept of barrier film and collector, positive pole as shown in Figure 1 with electrode 10 and negative pole 20 be the present invention lithium ion battery electrode.
Positive pole 10 is the pellet electrode with appointed thickness t1, its have be arranged at the side of barrier film 30 the 1st interarea 11 and It is arranged at the 2nd interarea 12 of the side of collector 40.Contain positive active material particle 14 in positive pole 10.
Similarly, negative pole 20 is the pellet electrode for having appointed thickness t2, and it has the 1st interarea for being arranged on the side of barrier film 30 21 and it is arranged on the 2nd interarea 22 of the side of collector 50.Negative pole 20 contains negative electrode active material particle 24.
The thickness t1 of the positive pole 10 and thickness t2 of negative pole 20 is respectively 50~5000 μm, as described above, when electrode is thicker, More active material can be contained in battery, lithium ion cell high-capacity can be made.
The lithium ion battery of the present invention is preferably 150~1500 μm with the thickness t1 of positive pole, more preferably 200~950 μm, More preferably 250~900 μm.
The thickness t2 of the negative electrode for lithium ion battery of the present invention is preferably 150~1500 μm, more preferably 200~950 μm, More preferably 250~900 μm.
It is as described above this hair by the lithium ion battery that the lithium ion battery of the present invention is used as negative pole and/or positive pole with electrode Bright lithium ion battery.
Then, the lithium ion battery of the present invention is illustrated with electrode.
Fig. 2 is the schematic cross-section for the positive pole for only representing the lithium ion battery shown in Fig. 1.
As described above, positive pole 10 has the 1st interarea 11 and the 2nd interarea 12.Also, the 1st interarea 11 and the 2nd interarea 12 it Between, include the chopped fiber (A) and long fibre (B) as conducting fibre.In fig. 2, chopped fiber (A) mark referring to the drawings 13A represents that long fibre (B) is represented with mark 13B referring to the drawings.
Between the 1st interarea 11 and the 2nd interarea 12, further containing the positive electrode active material as active material particle (C) Plasmid 14.
Chopped fiber 13A and long fibre 13B is that discrete existing electric conductivity is fine between the 1st interarea 11 and the 2nd interarea 12 Dimension.
In the lithium ion battery electrode of the present invention, at least a portion shape preferably in chopped fiber (A) and long fibre (B) Active matter plasmid around the conductive path that the interareas of Cheng Cong 1 are electrically connected to the 2nd interarea, conductive path and conductive path Sub (C) contact.
At least a portion in chopped fiber 13A and long fibre 13B is illustrated to be formed to enter from the 1st interarea to the 2nd interarea in Fig. 2 The mode of the conductive path of row electrical connection.
Represent that more of its length short long fibre 13B and chopped fiber 13A is heavy mutually compared with the thickness of electrode in Fig. 2 Close, form the mode of conductive path.
Also, the chopped fiber 13A or long fibre 13B positioned at an end of conductive path reach the 1st interarea 11, positioned at leading The chopped fiber 13A or long fibre 13B of another end of electric pathway reach the 2nd interarea 12.
In addition, 1 root long fiber 13B can connect the end and another end of conductive path.
In addition, it is also represented by Fig. 2 by chopped fiber 13A and long fibre the 13B conductive path formed and the work of the positive pole of surrounding Property material particle 14 contact mode.
Determine the fiber length distribution of conducting fibre contained in the lithium ion battery electrode of the present invention, 50nm with At least one peak be present in upper and less than 100 μm regions, more than 100 μm and be less than 1000 μm region exist it is at least one Peak.
In these cases, it can be determined that, chopped fiber (A) and long fibre are contained in the lithium ion battery electrode of the present invention Tie up (B).
The fibre length of conducting fibre can be observed by SEM to determine.
Firstly, for fiber present in the 0.2mm square visual field, fibre length is determined respectively, for more than 50nm and small In 100 μm of fiber, making fibre length is transverse axis, and measurement result (radical of fiber) is the frequency curve of the longitudinal axis, makes fiber Distribution of lengths carries out frequency curve.
In addition, the measure of fibre length is carried out with three visuals field, frequency curve is made with the total in three visuals field.
In addition, for fiber present in the 2mm square visual field, respectively three visuals field are carried out with the measure of fibre length, it is right In more than 100 μm and it is less than 1000 μm of fiber, with 50nm less than making dimension distribution of lengths in the same manner as 100 μm of fiber Carry out frequency curve.
Furthermore, it is possible to will be combined with the measurement result of 0.2mm visuals field square and with the measurement result of 2mm visuals field square, with One frequency curve records fiber length distribution, when being recorded with a frequency curve, as long as carrying out conversion makes measurement result (fiber Radical) ratio meet.
In addition, stretched out for one end from the visual field, so as to the unascertainable long fibre of fibre length, without counting.
Then, in 50nm less than in peak existing for 100 μm of region, by the fibre length (pattern that frequency is maximum Length) chopped fiber (A) average fiber length is set to, by the frequency more than 100 μm and existing for less than 1000 μm of region Maximum fibre length (modal length) is set to long fibre (B) average fiber length.
In addition, the fibre length as transverse axis when making frequency curve is recorded with following interval, to measurement result page Arranged according to the interval.
50nm~500nm：At intervals of 50nm
500nm~1 μm：At intervals of 100nm
1 μm~100 μm：At intervals of 10 μm
100 μm~500 μm：At intervals of 50 μm
500 μm~1000 μm：At intervals of 100 μm
In addition, two or more conducting fibres, used conduction are used in the manufacture of lithium ion battery electrode Property fiber species (model) and average fiber length it is known in the case of, can be without said determination, and from being used The value of average fiber length of conducting fibre judge whether containing chopped fiber (A) and long fibre (B).
Chopped fiber (A) is that average fiber length is 50nm less than 100 μm of conducting fibre, its average fiber length The preferred scope of degree is 500nm~50 μm, and preferred scope is 5 μm~30 μm.
The electrical conductivity of chopped fiber (A) is preferably more than 50mS/cm, more preferably 80mS/cm~500kS/cm, further excellent Elect 80~600mS/cm as.The electrical conductivity of chopped fiber (A), by based on JIS R 7609 " carbon fiber-specific insulation is asked Method ", specific insulation is measured, obtains the inverse of specific insulation and obtain.
When the electrical conductivity of chopped fiber (A) is more than 50mS/cm, formed from the 1st interarea to the 2nd interarea by chopped fiber (A) The resistance during conductive path of row electrical connection is small, and the movement of the electronics from the active material remote apart from collector is more successfully entered OK, therefore it is preferred that.
The avarage fiber diameter of chopped fiber (A) is preferably 0.01~20 μm, more preferably 0.05~2.0 μm.
The fibre diameter of chopped fiber (A) is observed by SEM to determine.For chopped fiber (A) avarage fiber diameter, Present in the 0.2mm square visual field, fibre length be 50nm less than 100 μm of fiber 10, measure center is attached respectively Near diameter, the measure is carried out with three visuals field, the average value of 30 fibre diameters will be amounted to as measured value.
Long fibre (B) is that average fiber length is more than 100 μm and is less than 1000 μm of conducting fibre, its average fibre The preferred scope for tieing up length is 110 μm~600 μm, and preferred scope is 150 μm~500 μm.
The electrical conductivity of long fibre (B) is preferably more than 50mS/cm, more preferably 80mS/cm~500kS/cm, further excellent Elect 80~200mS/cm as.The electrical conductivity of long fibre (B) can be obtained in the same manner as the electrical conductivity of chopped fiber (A).
When the electrical conductivity of long fibre (B) is more than 50mS/cm, formed by long fibre (B) from the 1st interarea to the 2nd interarea machine The resistance during conductive path of tool ox electrical connection is small, and the movement of the electronics from the active material remote apart from collector is more successfully Carry out, therefore it is preferred that.
The avarage fiber diameter of long fibre (B) is preferably 0.1~100 μm, more preferably 0.5~2.0 μm.
The fibre diameter of long fibre (B) is observed by SEM to determine.It is right for long fibre (B) avarage fiber diameter In present in the 2mm square visual field, fibre length be more than 100 μm and be less than 1000 μm fiber 10, determine respectively Diameter near center, the measure is carried out with three visuals field, the average value of diameter of 30 fibers will be amounted to as measured value.
In addition, two or more conducting fibres, used conduction are used in the manufacture of lithium ion battery electrode Property fiber species (model) and avarage fiber diameter it is known in the case of, can be without said determination, and will use The value of the avarage fiber diameter of conducting fibre is as chopped fiber (A) and the avarage fiber diameter of long fibre (B).
On the basis of the volume of electrode, the ratio of the volume shared by chopped fiber (A) is preferably 0.1~15vol%, more preferably For 0.5~5vol%.
On the basis of the volume of electrode, the ratio of the volume shared by chopped fiber (A) is exported by following formula.
[on the basis of the volume of electrode, the ratio of the volume shared by chopped fiber (A)] [%]=
[(weight of chopped fiber (A) used in unit area electrode)/(proportion of chopped fiber (A))]/[(list of electrode Plane accumulates) × (thickness of electrode)] × 100
It is 50nm less than 100 μm by fibre length in addition, when obtaining the ratio of the volume shared by chopped fiber (A) Fiber as chopped fiber (A).
On the basis of the volume of electrode, the ratio of the volume shared by long fibre (B) is preferably 0.001~15vol%, more excellent Elect 0.1~3vol% as.
In addition, on the basis of the volume of electrode, the ratio of the volume shared by long fibre (B), exported by following formula.
[on the basis of the volume of electrode, the ratio of the volume shared by long fibre (B)] [%]=
[(weight of long fibre (B) used in unit area electrode)/(proportion of long fibre (B))]/[(list of electrode Plane accumulates) × (thickness of electrode)] × 100
In addition, when obtaining the ratio of the volume shared by long fibre (B), it is more than 100 μm by fibre length and is 1000 μm Following fiber is as long fibre (B).
In addition, two or more conducting fibres, the electric conductivity used are used in the manufacture of lithium ion battery electrode In the case of the species (model) of fiber, proportion and usage amount (weight) are known, can be 50nm by average fiber length with Upper and less than 100 μm conducting fibres are set to chopped fiber (A), by average fiber length be more than 100 μm and be 1000 μm with Under fiber be set to long fibre (B), obtain the ratio of chopped fiber (A) and the volume shared by long fibre (B).
As described above, " ratio of the volume shared by the ratio and long fibre (B) of the volume shared by selection chopped fiber (A) " Refer to, preferably in electrode chopped fiber (A) and volume shared by long fibre (B) compared with active material particle (C) relatively It is few.
" ratio of the volume shared by the ratio and long fibre (B) of the volume shared by chopped fiber (A) is few " refers to, active matter In the space that plasmid (C) is filled in chopped fiber (A) and long fibre (B) does not occupy, due to filling active material particle (C), As the lithium ion battery electrode of high power capacity.
In addition, in the lithium ion battery electrode of the present invention, on the basis of the volume of electrode, active material particle (C) The ratio of shared volume is preferably 30~80vol%, more preferably 40~60vol%.By making active material particle (C) Ratio becomes more, turns into the lithium ion battery electrode of high power capacity.
In the lithium ion battery electrode of the present invention, the volume (V shared by chopped fiber (A)A) with long fibre (B) shared by Volume (VB) ratio (VA/VB) it is preferably 0.2~50, more preferably 0.25~5.
In addition, in the lithium ion battery electrode of the present invention, the volume (V shared by chopped fiber (A)A) and long fibre (B) volume (V shared byB) total (VA+VB) with active material particle (C) shared by volume (VC) ratio [(VA+VB)/VC] Preferably 0.00125~0.5, more preferably 0.02~0.3.
By making the volume (V shared by chopped fiber (A)A) and long fibre (B) shared by volume (VB) less, so as to big portion It is divided into active material particle (C), turns into the lithium ion battery electrode of high power capacity.
In addition, volume (the V shared by chopped fiber (A)A), the volume (V shared by long fibre (B)B) and active material particle (C) volume (V shared byC) determined by following method.
Electrolyte etc. is dried, the electricity to being mixed with chopped fiber (A), long fibre (B) and active material particle (C) Pole 1cm2Weight [w (g)] and the thickness [t (cm)] of electrode be measured, from chopped fiber (A) true specific gravity [dA (g/ cm3)], the true specific gravity [dB (g/cm of long fibre (B)3)], the true specific gravity [dC (g/cm of active material particle (C)3)] and short fibre Tie up (A), long fibre (B) and active material particle (C) relative to the gross weight for the material for forming electrode of the present invention addition ratio Example (WA, WB, WC) calculates.
VA=(w × WA/dA)/(t × 1) × 100
VB=(w × WB/dB)/(t × 1) × 100
VC=(w × WC/dC)/(t × 1) × 100
As chopped fiber (A) and the conducting fibre of long fibre (B), it is fine that PAN based carbon fibers, pitch class carbon can be included The carbon fibers such as dimension, make the metal of good conductivity or graphite be dispersed in formed in synthetic fibers conducting fibre, to such as The metal of stainless steel carries out the metallic fiber that fibrosis forms, the surfaces of organic fibres is led with what metal carried out that cladding forms Conductive fiber, the conducting fibre for forming on the surface of organic fibres with the resin-coating containing conductive material etc..These In conducting fibre, preferred carbon fiber.
Positive active material particle 14 is the active material particle (C) of the lithium ion battery electrode of the present invention.As just Pole active material particle, composite oxides (such as the LiCoO of lithium and transition metal can be included2、LiNiO2、LiMnO2And LiMn2O4And LiNi0.8Co0.15Al0.05O2Deng lithium nickel composite oxide), transition metal oxide (such as MnO2And V2O5), transient metal sulfide (such as MoS2And TiS2) and electroconductive polymer (such as polyaniline, poly- inclined difluoro second Alkene, polypyrrole, polythiophene, polyacetylene, polyparaphenylene and polycarbazole) etc..
In addition, LiNi0.8Co0.15Al0.05O2It is the composite oxides shown in following formulas (1) Deng lithium nickel composite oxide,
Formula (1)：Lix(Ni1-yCoy)1-zMzO2(wherein, in formula, x, y, z is：0.98≤x≤1.10、0.05≤y≤ 0.4th, 0.01≤z≤0.2, M are selected from least one of Al, Mg, Mn, Ti, Fe, Cu, Zn and Ga metallic element) represent Compound.
As its preferable example, lithium-nickel-manganese-cobalt composite oxide or lithium-nickel-cobalt-aluminum composite oxide can be included Thing etc..
In the lithium ion battery electrode of the present invention, active material particle (C) is preferably at least a portion quilt on surface The cladding active material particle formed containing the covering of cladding resin and conductive auxiliary agent cladding.
In fig. 2 in shown mode, agent 15 is wrapped by around positive active material particle 14 and is coated.Covering contains There is cladding resin, when having carried out cladding by covering around positive active material particle, the Volume Changes of electrode are alleviated, The expansion of electrode can be suppressed.As the example of cladding resin, vinylite, polyurethane resin, polyester tree can be included Fat, polyamide, epoxy resin, polyimide resin, organic siliconresin, phenolic resin, melmac, urea tree Fat, anline resin, ionomer resin, makrolon etc..In them, preferred vinyl resin, polyurethane resin, polyester resin or Polyamide.
In the lithium ion battery electrode of the present invention, active material particle (C) is used as using cladding active material particle When, lithium ion battery electricity consumption is highly preferred without binding agent (also referred to as adhesive).As binding agent said here, can include It is viscous between the bonding and active material particle of active material particle and collector in the electrode of lithium ion battery Become known binding agent (starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrole that purpose uses The high-molecular compounds such as alkanone, tetrafluoroethene, SBR styrene butadiene rubberses, polyethylene and polypropylene) etc..
, it is necessary to pass through profit in the lithium ion battery electrode using the active material particle of non-cladding active material particle Active material particle is fixed in electrode with binding agent, thus maintains conductive path.But use cladding active material particle When, because cladding is acted on resin, active material particle can not be fixed in electrode and maintain conductive path, because This, not necessarily needs to add binding agent.Due to not adding binding agent, active material particle is not immobilized in electrode, because This, mitigation ability of the active material particle for Volume Changes becomes good.
The conductive path formed by chopped fiber 13A and long fibre 13B, with the positive electrode active material plasmid around conductive path Son 14 connects.When conductive path connects with positive active material particle, from electronics caused by positive active material particle quickly to Up to conductive path, conductive path is flowed through, to reaching collector.Because conductive path is by the electric conductivity as electronic conductivity material Fiber is formed, and therefore, electronics can successfully arrive and reach collector.
In addition, when active material particle is coats active material particle, when covering connects with conductive path, can be considered as Conductive path contacts with active material particle.
In the electrode without conductive path, because electronics must pass through the not high active matter plasmid of electronic conductivity Son, therefore electronics is difficult to successfully reach collector.In addition, in the electronics conduction that have passed through the conductive auxiliary agent as particulate matter In, interparticle resistance be present, the particle of conductive auxiliary agent is not continuously connected, and therefore, electronics is had to high by resistance Position.Therefore, electronics is difficult to successfully reach collector.
In addition, in the above description, in case of reaching collector from electronics caused by positive active material particle, The motion of electronics is illustrated, still, the electronics moved from collector to positive active material particle similarly can be by leading Electric pathway, successfully arrive and reach positive active material particle.That is, in charging and the when of electric discharge, can obtain same effect.
In addition, it can further contain conductive auxiliary agent 16 in positive pole 10.
As conductive auxiliary agent, selected from conductive material.
Specifically, [aluminium, stainless steel (SUS), silver, gold, copper and titanium etc.], carbon [graphite and carbon black (acetylene can be included Black, Ketjen black, furnace black, channel black, thermolamp are black etc.) etc.] and these mixture etc., but it is not limited to this.
These conductive auxiliary agents can be used alone, and can also be applied in combination two or more.Alternatively, it is also possible to use this A little alloys or metal oxide.From the viewpoint of electric stability, preferably aluminium, stainless steel, carbon, silver, gold, copper, titanium with And their mixture, it is more preferably silver, gold, aluminium, stainless steel and carbon, more preferably carbon.In addition, these conductions help Agent or by conductive material (metal material in the material of above-mentioned conductive auxiliary agent) plating spread on particle class ceramic material Or the conductive auxiliary agent that coating forms around resin material etc..
In addition, conductive auxiliary agent 16 may be embodied in covering 15, conductive auxiliary agent 16 can be with positive active material particle 14 connect.By making conductive auxiliary agent be included in covering, or connect with positive active material particle, can further improve from Positive active material particle reaches the electronic conductivity of conductive path.
The present invention lithium ion battery electricity consumption extremely negative pole when, be used as active material particle using negative electrode active material particle (C) positive active material particle is replaced, in addition, same composition can be set to.
As negative electrode active material particle, graphite, difficult graphitized carbon, agraphitic carbon, high-molecular compound can be included and burnt Knot body (such as sintered body that phenolic resin and furane resins etc. are sintered and are carbonized etc.), coke class (such as drip Blue or green coke, needle coke and petroleum coke etc.), carbon fiber, electroconductive polymer (such as polyacetylene and polypyrrole etc.), tin, Silicon and metal alloy (such as lithium-tin alloy, lithium-silicon alloy, lithium-aluminium alloy and lithium-aluminum-manganese alloy etc.), lithium and transition Composite oxides (such as the Li of metal4Ti5O12Deng) etc..
In negative pole, because conductive path connects with the negative electrode active material particle around conductive path, therefore, with positive pole Situation it is identical, quickly reach conductive path from electronics caused by negative electrode active material particle, pass through conductive path, smoothly reach To collector.In addition, the electronics moved from collector to negative electrode active material particle also can be quickly to reaching negative electrode active material Matter.
In addition, in the lithium ion battery electricity consumption extremely negative pole of the present invention, activity is used as using cladding active material particle During material particle (C), preferably lithium ion battery is free of binding agent with electrode.Its reason and lithium ion battery electricity consumption extremely positive pole when It is identical.
The lithium ion battery of the invention of mode shown in Fig. 2 is following electrode with electrode：Chopped fiber (A) and long fibre Dimension (B) and active material particle (C) are fixed on film (E), the shape being maintained in the form of the degree that will not flow smoothly its State.When film (E) is formed by the high material of electric conductivity (conductive material), collector can be replaced using film (E), in addition, even if Collector is set to be contacted with film (E), electric conductivity is also unobstructed, therefore it is preferred that.Film (E) is not shown in FIG. 2.On chopped fiber (A) And long fibre (B) and active material particle (C) are fixed on the manufacturer of the lithium ion battery electrode formed on film (E) Method, behind describe in detail.
Then, the lithium ion battery of the present invention is illustrated with the manufacture method of electrode.
The lithium ion battery of the present invention is lithium ion battery electricity consumption of the invention with a mode of the manufacture method of electrode The manufacture method of pole, it is characterised in that including：Process (Q1), will include above-mentioned chopped fiber (A), above-mentioned long fibre (B) and on The slurry (Y) for stating active material particle (C) is coated on film (E)；And process (Q2), pressurizeed or depressurized, by above-mentioned work Property material particle (C), above-mentioned chopped fiber (A) and above-mentioned long fibre (B) are fixed on above-mentioned film (E).
The manufacture method of aforesaid way is suitable for lithium ion battery electrode of the manufacture using Fig. 2 modes illustrated.Especially It is the positive pole for being more suitable for manufacturing lithium ion battery.
Fig. 3 (a) and Fig. 3 (b) is fixed on chopped fiber and long fibre and active material particle to schematically show The process chart of process on film.
First, the slurry (Y) comprising chopped fiber (A), long fibre (B) and active material particle (C) is coated on film (E) Upper (process Q1).
As slurry (Y), the slurry formed as follows can be included：In the slurry (X) containing active material, further add Enter chopped fiber (A) and long fibre (B), make chopped fiber (A) and long fibre (B) scattered in the slurry.
As active material particle (C), it can use what is illustrated in the explanation of the lithium ion battery electrode of the present invention It is preferable to use cladding active material particle for active material particle (C).Active material particle is coated following can for example to obtain Arrive：Lithium ion battery active material particle is added to universal mixer, in the state of 30~500rpm stirrings, last 1~ 90 minutes with the resin solution of resin containing lithium ion battery active material cladding to carrying out dropwise addition mixing, further hybrid conductive Auxiliary agent, 50~200 DEG C, after being decompressed to 0.007~0.04MPa are warming up in the state of stirring, are kept for 10~150 minutes and obtained Arrive.
Slurry (X) comprising active material particle (C) is preferably the solvent slurry (X1) for including solvent (F), or includes electricity Solve the electrolyte paste (X2) of liquid (D).
As solvent (F), water outlet, 1-Methyl-2-Pyrrolidone (1-METHYLPYRROLIDONE), MEK, diformazan can be enumerated Base formamide, dimethyl acetamide, N, N- dimethylaminopropylamines and tetrahydrofuran etc..
In addition, as electrolyte (D), it can use what is used in the manufacture of lithium ion battery to contain electrolyte and non- The electrolyte of aqueous solvent.
As electrolyte, electrolyte generally used in the electrolytic solution etc. can be used, for example, LiPF can be included6、 LiBF4、LiSbF6、LiAsF6And LiClO4Deng the lithium salts of inorganic acid；LiN(CF3SO2)2、LiN(C2F5SO2)2And LiC (CF3SO2)3Lithium salts Deng organic acid etc..Wherein, from the viewpoint of cell output and charge/discharge cycle characteristics, preferably LiPF6。
As nonaqueous solvents, nonaqueous solvents used in usual electrolyte etc. can be used, such as lactone compound can be used Thing, ring-type or linear carbonate, chain carboxylate, ring-type or chain ether, phosphate, nitrile compound, amide compound, sulfone, ring Fourth sulfone etc. and their mixture.
Nonaqueous solvents can be used alone, can also be simultaneously using two or more.
In nonaqueous solvents, from the viewpoint of cell output and charge/discharge cycle characteristics, preferably lactone compound, Cyclic carbonate, linear carbonate and phosphate, more preferably lactone compound, cyclic carbonate and linear carbonate, enter The mixed liquor of the preferred cyclic carbonate of one step and linear carbonate.Particularly preferred ethylene carbonate (EC) and diethyl carbonate (DEC) mixed liquor.
Slurry (X) preferably by by active material particle (C) and the conductive auxiliary agent and binding agent that are added as needed on, Weight based on solvent or electrolyte is scattered and slurried and prepare with 10~60 weight % concentration.
As conductive auxiliary agent, the conduction illustrated in the explanation of lithium ion battery of the invention with electrode can be used to help Agent.
As binding agent, starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrole can be included The high-molecular compounds such as alkanone, tetrafluoroethene, SBR styrene butadiene rubberses, polyethylene and polypropylene.
In addition, when using cladding active material particle as active material particle (C), preferably do not added in slurry (X) Binding agent., it is necessary to utilize viscous in the lithium ion battery electrode using the active material particle of non-cladding active material particle Active material particle is fixed in electrode and maintains conductive path by knot agent.But during using cladding active material particle, due to Cladding carries out that effect can maintain conductive path with resin and active material particle is not fixed in electrode, therefore need not add Binding agent.Due to not adding binding agent, active material particle not being fixed in electrode, therefore, active material particle pair Become good in the mitigation ability of Volume Changes.
As chopped fiber (A) and long fibre (B), it can use and be said in the page of lithium ion battery of the invention with electrode Bright chopped fiber (A) and long fibre (B).
Slurry (Y) is preferably the electrolyte paste (Y1) containing electrolyte (D).As electrolyte (D), can use with it is upper State electrolyte (D) identical electrolyte in electrolyte paste (X2).Slurry (Y) is the electrolyte paste containing electrolyte (D) (Y1) when, the impurity that the liquid component in as lithium ion battery electrode will not be mixed into addition to electrolyte is excellent on this point Choosing.
In addition, slurry (Y) can also be the solvent slurry containing solvent (F).
, can be by active material particle and conductive component preferably in pressurization afterwards or decompression process as film (E) The film separated with electrolyte and solvent.In addition, when film (E) is formed by the high material of electric conductivity (conductive material), can make Collector is replaced with film (E), in addition, even if making collector be contacted with film (E), electric conductivity will not be also obstructed, therefore it is preferred that.Example Such as it is preferable to use the material that electrical conductivity is more than 100mS/cm.
As the example for the material having characteristics that, the filter added with conducting fibres such as carbon fibers can be included Paper, wire netting etc..
As wire netting, preferably using stainless steel net, such as SUS316 twill can be included and folded knit woven wire (manufacture of SUNNET Industrial Co., Ltd) etc..The mesh of wire netting preferably passes through active material particle and conductive component Degree, such as preferably use 2300 mesh net.
Slurry (Y) can be coated on film (E) using the arbitrary apparatus for coating such as rod coater, brush.
The mode that slurry is coated with film is shown schematically in Fig. 3 (a), is coated with the filter paper 470 as film Slurry comprising positive active material particle 14 Yu chopped fiber 13A and long fibre 13B.
Then, pressurizeed or depressurized, active material particle (C), chopped fiber (A) and long fibre (B) is fixed on film (E) on (process Q2).
As the method for pressurized operation, the method suppressed from the coated face of slurry using press can be included. In addition, the method as decompression operation, can enumerate the surface that send as an envoy to filter paper or net etc. are connected to the uncoated slurry side of structure On, pass through the method for vavuum pump attraction.
Electrolyte or solvent are removed by being pressurizeed or being depressurized from slurry (Y), by chopped fiber (A) and long fibre (B) It is fixed on active material particle (C) on film (E), the degree for turning into not flow smoothly maintains the state of its shape.
Show chopped fiber 13A and long fibre 13B and positive active material particle 14 being fixed on filter paper 470 in Fig. 3 (b) Upper and formation electrode 210.
When film (E) is formed by conductive material in electrode 210, film (E) may be used as collector, furthermore it is possible to make collection Electric body and film (E) contact, plays a role as a collector.That is, in electrode 210, the 2nd interarea 212 can be used as short Fiber 13A and/or long fibre 13B determines with part that filter paper 470 contacts.
When film (E) is the material without electric conductivity, film (E) can be arranged on barrier film side.Furthermore it is possible to by film (E) As barrier film.As the example of the film formed by the material without electric conductivity, (the Japanese VILENE strains of aramid fiber barrier film can be included Formula commercial firm manufactures) etc..
In addition, when slurry (Y) is electrolyte paste (Y1) containing electrolyte (D), film (E) is to pass through electrolyte (D) Without the film for passing through active material particle (C), in process (Q2), preferably pressurizeed or depressurized, pass through electrolyte (D) Film (E) and remove.
Additionally, it is preferred that after process (Q2), suppression process (Q3) is carried out：Slurry (Y) is pressurizeed with stronger pressure.
Suppression process (Q3) further increases pressure differential compared with the pressurization or decompression in process (Q2), improves active matter The density of plasmid (C).Suppression process (Q3) is the mode for applying pressurization in the case where process (Q2) is decompression；And process (Q2) in the case of for pressurization, the concept of both modes for the pressure for further improving pressurization.
Also, it is preferred that carry out process (Q4)：By the lithium ion battery being fixed on film (E) with electrode be transferred to collector or The interarea of barrier film, form the lithium ion battery electrode that lithium ion battery is arranged on the interarea of barrier film with the 1st interarea of electrode；Or Person, form the lithium ion battery electrode that lithium ion battery is arranged on the interarea of collector with the 2nd interarea of electrode.
When carrying out process (Q4), the side opposite with film (E) of lithium ion battery electrode that preferably makes to be fixed on film (E) Interarea [the 1st interarea 211 in Fig. 3 (b)] is contacted and shifted with the interarea of collector or barrier film.
Film (E) is formed by conductive material, when replacing collector using film (E), is preferably made and the master of film (E) opposite side Face contacts and shifted with the interarea of barrier film.In addition, when film (E) not being used as into collector, preferably after process (Q4) has been carried out, enter The process of row stripping film (E).
The lithium ion battery of the present invention is lithium ion battery electricity consumption of the invention with the other modes of the manufacture method of electrode The manufacture method of pole, it is characterised in that including：Process (T1), will include above-mentioned chopped fiber (A), above-mentioned long fibre (B) and on Slurry (Y) coating for stating active material particle (C) on the current collector, forms pulp layer on the current collector；And process (T2), Barrier film is loaded on above-mentioned pulp layer, imbibition is carried out from the upper surface side of barrier film, by above-mentioned active material particle (C), above-mentioned short Fiber (A) and above-mentioned long fibre (B) are fixed between above-mentioned collector and above-mentioned barrier film.
The manufacture method of aforesaid way, it is suitable for lithium ion battery electrode of the manufacture using Fig. 2 modes illustrated.Especially It is the negative pole for being more suitable for manufacturing lithium ion battery.
Fig. 4 (a), Fig. 4 (b) and Fig. 4 (c) are to show schematically active material particle, chopped fiber and long fibre The process chart for the process being fixed between collector and barrier film.
First, the slurry (Y) comprising chopped fiber (A), long fibre (B) and active material particle (C) is coated on current collection On body, pulp layer (process T1) is formed.
As collector, aluminium, copper, aluminium, titanium, stainless steel, nickel, calcining carbon, electroconductive polymer and conduction can be included Property glass etc..
As slurry (Y), slurry (Y) identical slurry with using Fig. 3 (a) to illustrate can be used, can include and starch Expect further to add chopped fiber (A) and long fibre (B) in (X), make chopped fiber (A) and long fibre (B) scattered in the slurry And the slurry formed.
Slurry (Y) is preferably the electrolyte paste (Y1) containing electrolyte (D).As electrolyte (D), can use with it is upper Electrolyte (D) identical electrolyte in the electrolyte paste (X2) stated.In addition, slurry (Y) can be to contain the molten of solvent (F) Agent slurry.
Slurry (Y) can use the arbitrary apparatus for coating coating such as rod coater, brush on the current collector.
The coating sizing-agent on collector 50 is shown schematically in Fig. 4 (a), the mode of pulp layer 225 is formed, in collector Coating includes negative electrode active material particle 24 and chopped fiber 13A and long fibre 13B slurry on 50, forms pulp layer 225.
In the mode shown in Fig. 4 (a), agent 25 is wrapped by around negative electrode active material particle 24 and is coated, is contained in slurry There is conductive auxiliary agent 26.
On chopped fiber 13A, long fibre 13B, covering 25 and conductive auxiliary agent 26, respectively with the lithium ion in the present invention Illustrate that the chopped fiber 13A of its details, long fibre 13B, covering 15, conduction help in the explanation of electrode for cell (positive pole) Agent 16 is identical.
In addition, negative electrode active material particle 24 in explanation of the lithium ion battery of the present invention with electrode with illustrating that its is detailed The negative electrode active material particle of details condition is identical.
Then, barrier film is loaded on pulp layer, imbibition is carried out from the upper surface side of barrier film, by active material particle (C) and Chopped fiber (A) and long fibre (B) are fixed between collector and barrier film (process T2).First, as shown in Fig. 4 (b), in slurry Barrier film 30 is loaded on layer 225.Then, imbibition is carried out from the upper surface side of barrier film 30.
As barrier film, aramid fiber barrier film (Japanese VILENE Co., Ltd. manufacture) can be included；Polyethylene, polypropylene are film-made Micro-porous film；Porous polyethylene film and polyacrylic multilayer film；Formed by polyester fiber, aramid fiber, glass fibre etc. Non-woven fabrics；And there is film that the ceramic particles such as silica, aluminum oxide, titanium dioxide form etc. in their surface attachment.
Imbibition can be carried out as follows：Pressurizeed from the upper surface side or lower face side of barrier film, to from the upper surface of barrier film The liquid of leaching carries out imbibition, alternatively, it is also possible to by being depressurized from the upper surface side of barrier film, attract liquid and carry out.Also By placing liquid absorbent material in the upper surface of barrier film imbibition can be carried out from the upper surface side of above-mentioned barrier film.
As liquid absorbent material, absorbency cloth, paper, the absorbency resins such as towel etc. can be used.
Electrolyte or solvent, chopped fiber (A) and long fibre (B) and active matter are removed from slurry (Y) by imbibition Plasmid (C) is fixed between collector and barrier film, the degree shape that smoothly its shape is maintained for being formed to flow State.
The method of pressurization is simultaneously not specifically limited, and various methods can be utilized to implement.For example, it can include known to use The method of press and the method that weight thing etc. is loaded as counterweight and is pressurizeed, pressurization can also utilize ultrasonic activation machine Shaken Deng adding while carrying out.It is preferably 0.8~41kg/cm from pressure when upper surface side or the lower face side pressurization of barrier film2, More preferably 0.9~10kg/cm2.Pressure can form the conductive path of electrode interior well in the scope, accordingly, it is capable to Enough make the further high capacity of battery, therefore it is preferred that.
Fig. 4 (c) show by chopped fiber 13A and long fibre 13B and active material particle 24 be fixed on collector 50 with The electrode 220 formed between barrier film 30.
In electrode 220, the 1st interarea 221 of electrode connects with barrier film 30, the 2nd interarea 222 and the phase of collector 50 of electrode Connect.
For lithium ion battery electrode as described above manufacture method when, the state clamped with electrode by barrier film and collector Manufactured.It therefore, there is no need to separately carry out the process for setting barrier film and collector in the both sides of electrode, with bipolar electrode Form can obtain the electrode of preferred embodiment with less process, therefore it is preferred that.
The lithium ion battery of the present invention has been used to be obtained as follows with the lithium ion battery of electrode：Combination is as the electricity to electrode Pole, it is accommodated in together with barrier film in battery case, injects electrolyte, sealed battery container.
In addition, by forming positive pole on a surface of collector, negative pole is formed on another surface, makes ambipolar electricity Pole, lamination is carried out to bipolar electrode and barrier film, is accommodated in battery case, injects electrolyte, sealed battery container and obtain.
In addition, any electrode can use the lithium ion battery electrode of the present invention, also positive pole, negative pole in positive pole, negative pole Lithium ion battery can be made in the form of electrode by the lithium ion battery of the present invention simultaneously.
As barrier film, polyethylene, the micro-porous film of polypropylene film can be included；Porous polyethylene film and polypropylene Multilayer film；The non-woven fabrics formed by polyester fiber, aramid fiber, glass fibre etc.；And have two in their surface attachment Film that the ceramic particles such as silica, aluminum oxide, titanium dioxide form etc..
As electrolyte, above-mentioned electrolyte can be used as electrolyte (D).
Embodiment
Specifically describe the present invention below by embodiment, but as long as do not depart from the present invention purport, the present invention not by It is defined in embodiment.In addition, in the case of without especially recording, part represents parts by weight, and % represents weight %.
The making ＞ of ＜ cladding resin solutions
In the four-hole boiling flask with mixer, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe, add Enter 17 parts of 83 parts of ethyl acetate and methanol, be warming up to 68 DEG C.Then, while being blown into nitrogen in four-hole boiling flask, while stirring It is lower to last 4 hours and be continuously added dropwise following monomer mixed solutions and by 2,2 '-azo two (2,4- methyl pentane nitriles) using dropping funel 0.263 part is dissolved in the initiator solution formed in 34.2 parts of ethyl acetate, carries out radical polymerization, and the monomer mixed solution leads to Cross 242.8 parts of cooperation methacrylic acid, 97.1 parts of methyl methacrylate, 242.8 parts of 2-Ethylhexyl Methacrylate, acetic acid 10.7 parts of 52.1 parts of ethyl ester and methanol and formed.After completion of dropwise addition, using dropping funel last 2 hours it is continuous additional by 2, 0.583 part of 2 '-azo two (2,4- methyl pentane nitriles) is dissolved in the initiator solution formed in 26 parts of ethyl acetate.Further, Continue polymerization 4 hours in boiling point.Solvent is removed, after obtaining 582 parts of resin, 1,360 parts of isopropanol is added, obtains by resin concentration The cladding resin solution that 30 weight % vinylite is formed.
The making ＞ of ＜ clad anodes active material particle (C-1)
By LiCoO2Powder [Nippon Chemical Ind's manufacture, CELLSEED C-8G] 96 parts by weight are put into omnipotent Mixer, at room temperature, in the state of being stirred with 150rpm, lasting 60 minutes, (resin is solid to cladding resin solution Body constituent concentration is 30 weight %) dropwise addition mixing is carried out, and make resin solid content be 2 parts by weight, further stir 30 minutes.
Then, in the state of stirring, by acetylene black [Deuki Kagaku Kogyo Co., Ltd's manufacture, the DENKA of 2 parts by weight BLACK (registration mark)] point 3 mixing, 70 DEG C are warming up in the state of having stirred 30 minutes, is decompressed to 100mmHg, is kept 30 minutes.By aforesaid operations, clad anode active material particle (C-1) is obtained.
The making ＞ of ＜ clad anodes active material particle (C-2)
By LiCoO2Powder [Nippon Chemical Ind manufacture CELLSEED C-8G] 96 parts by weight are changed to LiNi0.8Co0.15Al0.05O2Powder (being also recited as NCA below) powder, in addition, carry out same with the preparation method of (C-1) Operation, obtain clad anode active material particle (C-2).
The making ＞ of ＜ cladding negative electrode active material particles (C-3)
By the difficult graphitization carbon of 90 parts by weight [(strain) Kureha Battery Materials Japan manufactures, CARBOTRON (registration mark) PS (F)] universal mixer is put into, at room temperature, in the state of being stirred with 150rpm, Last 60 minutes and dropwise addition mixing is carried out with resin solution (resin solid content concentration is 30 weight %) to cladding, and consolidate resin Body composition is 5 parts by weight, further stirring 30 minutes.
Then, in the state of stirring, acetylene black [Deuki Kagaku Kogyo Co., Ltd's manufacture, the DENKA of 5 parts by weight BLACK (registration mark)] point 3 mixing, 70 DEG C are warming up in the state of having stirred 30 minutes, is decompressed to 0.01MPa, is kept 30 minutes.By aforesaid operations, obtain coating negative electrode active material particle (C-3).
The preparation ＞ of ＜ chopped fibers (A-1)
Chopped fiber (A-1) refers to Eiichi Yasuda, Asao Oya, Shinya Komura, Shigeki Tomonoh, Takashi Nishizawa, Shinsuke Nagata, Takashi Akatsu, CARBON, 50,2012,1432-1434 and Eiichi Yasuda, Takashi Akatsu, Yasuhiro Tanabe, Kazumasa Nakamura, Yasuto The manufacture method of Hoshikawa, Naoya Miyajima, TANSO, 255,2012,254~265 page and manufacture.
Using as the synthetic mesophase asphalt phase ARMPH of carbon precursor [manufacture of gas KCCs of Mitsubishi] 10 parts by weight It is 310 DEG C, nitrogen atmosphere in barrel temperature with polymethylpentene TPX RT18 [Mitsui Chemicals, Inc's manufacture] 90 parts by weight It is lower to carry out melting mixing using single axle extruding machine, prepare resin combination.
Melting extrusion is carried out to above-mentioned resin combination at 390 DEG C, and spinned.The resin group that will be spinned Compound is put into electric furnace, is kept for 3 hours in a nitrogen atmosphere, at 270 DEG C, stabilizes carbon precursor.Then, lasting 1 hour will Electric furnace is warming up to 500 DEG C, is kept for 1 hour at 500 DEG C, decomposes and removes polymethylpentene.2 hours are lasted to be warming up to electric furnace 1000 DEG C, kept for 30 minutes at 1000 DEG C, using the stabilized carbon precursor retained as conducting fibre.
By the obtained parts by weight of conducting fibre 90, the parts by weight of water 500 and Φ the 0.1mm parts by weight of zirconia ball 1000 Balling mill container is put into, is crushed 5 minutes.After zirconia ball is classified, it is dried at 100 DEG C, obtains chopped fiber (A-1).
From the measurement result obtained using SEM, avarage fiber diameter is 0.3 μm, and average fiber length is 26 μm.Separately Outside, the electrical conductivity of chopped fiber (A-1) is 600mS/cm.
The making ＞ of ＜ chopped fibers (A-2)
In above-mentioned chopped fiber (A-1) making, in addition to the condition that melting extrusion spins is changed, conduction is similarly obtained The chopped fiber (A-2) of property.
It was found from the measurement result obtained using SEM, avarage fiber diameter is 0.2 μm, and average fiber length is 9 μm.
In addition, the electrical conductivity of chopped fiber (A-2) is 600mS/cm.
The preparation ＞ of ＜ long fibres (B-1)
As long fibre, prepare carbonaceous carbon fiber [manufacture of Osaka Gas Chemicals Co., Ltd., DONACARBO Milled S-243：500 μm of average fiber length, 13 μm of avarage fiber diameter：Electrical conductivity 200mS/cm].
The preparation ＞ of ＜ long fibres (B-2)
As long fibre, prepare carbonaceous carbon fiber [manufacture of Osaka Gas Chemicals Co., Ltd., DONACARBO Milled S-344：960 μm of average fiber length, 18 μm of avarage fiber diameter：Electrical conductivity 200mS/cm].
The preparation ＞ of ＜ long fibres (B ' -1)
As long fibre, prepare graphite carbon fiber [manufacture of Osaka Gas Chemicals Co., Ltd., DONACARBO Milled SG-249：110 μm of average fiber length, 13 μm of avarage fiber diameter：Electrical conductivity 600mS/cm].
The preparation ＞ of ＜ long fibres (B ' -2)
As long fibre, prepare the graphite carbon fiber [XN- of Nippon Graphite Fiber Co., Ltd. manufacture 100-15M：150 μm of average fiber length, 10 μm of avarage fiber diameter：Electrical conductivity 600mS/cm].
The making ＞ of ＜ electrolyte
Make LiPF6The mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) is dissolved in 1mol/L ratio (volume ratio 1：1) in, electrolyte for lithium ion battery is made.
＜ embodiments 1：The making ＞ of positive pole
Using the parts by weight of chopped fiber (A-1) 2, the parts by weight of long fibre (B-1) 1 and 97 parts by weight as positive active material The LiCoO of particle2Powder [Nippon Chemical Ind's manufacture, CELLSEED C-8G] mixes with above-mentioned electrolyte, makes Electrolyte paste.
As film (E), preparing stainless steel net, [Sunnet Industrial Co., Ltd, which manufactures, SUS316 twills are close knits (twilled dutch weave), 2300 mesh], electrolyte paste is coated on above-mentioned stainless steel net, by attracting to filter (decompression), make positive active material particle and chopped fiber and long fibre to be fixed on stainless steel online, so as to make lithium ion Positive electrode for battery.
＜ embodiments 2~11 and the ＞ of comparative example 1~6
As shown in table 1, change chopped fiber (A), the species of long fibre (B) and active material (C), volume ratio and The thickness and weight per unit area of electrode, make lithium ion battery positive pole.
In table 1, LCO represents LiCoO2Particle, NCA represent LiNi0.8Co0.15Al0.05O2Particle, cladding LCO represent cladding LCO particles, cladding NCA represent cladding NCA particles.
＜ embodiments 12：The making ＞ of negative pole
Using the parts by weight of chopped fiber (A-1) 2, the parts by weight of long fibre (B-1) 4.2 and 93.8 parts by weight as negative electrode active Difficult graphitization carbon [manufacture of Kureha Battery Materials Japan Co., Ltd., the CARBOTRON of material particle (registration mark) PS (F)] mixed with above-mentioned electrolyte, make electrolyte paste.
As film (E), prepare aramid fiber barrier film (Japanese Vilene Co., Ltd. manufacture), electrolyte paste is coated on above-mentioned Aramid fiber barrier film, with moulding pressure 1.5kg/cm while filtering (decompression) by attraction2Pressurizeed, make negative electrode active material plasmid Son and carbon fiber are fixed on aramid fiber barrier film, make negative electrode for lithium ion battery.
＜ embodiments 13~22 and the ＞ of comparative example 7~11
As shown in table 2, change chopped fiber (A), the species of long fibre (B) and active material (C), volume ratio and The thickness and weight per unit area of electrode, make negative electrode for lithium ion battery.
In table 2, HC represents difficult graphitization carbon particle, and cladding HC represents to coat difficult graphitization carbon particle.
[making of positive pole evaluation lithium ion battery]
The positive pole made in arbitrary examples in embodiment 1~11 and comparative example 1~6 is punched into 17mm φ, with 17mm The φ negative pole formed by Li metals is arranged at the both ends in 2032 type button cells together.
As the collector of side of the positive electrode, using the aluminium electroloysis paper tinsel that thickness is 20 μm, stainless steel net is arranged at collector Side.
2 barrier films (Celgard 3501) are inserted between electrode, make lithium ion battery battery.
Fluid injection sealing is carried out to above-mentioned electrolyte in the battery, discharge capacity (mAh) is determined using following method, divided by The weight of active material, evaluated in a manner of the discharge capacity (mAh/g) of active unit weight.
The battery made during this is evaluated is as evaluation electricity pool 1~11 and compares with battery 1~6.
[making of negative pole evaluation lithium ion battery]
The negative pole made in arbitrary examples in embodiment 12~22 and comparative example 7~11 is punched into 17mm φ, with The 17mm φ positive pole formed by Li metals is arranged at the both ends in 2032 type button cells together.
As the collector of negative side, using the copper foil that thickness is 20 μm, aramid fiber barrier film is arranged at barrier film side (positive pole Side).
2 barrier films (Celgard 3501) are inserted between electrode, make lithium ion battery battery.In the battery to above-mentioned Electrolyte carries out fluid injection sealing, and discharge capacity (mAh) is determined using following method, and divided by active material weight, with work The mode of the discharge capacity (mAh/g) of property material Unit Weight is evaluated.
The battery made during this is evaluated is as evaluation electricity pool 12~22 and compares with battery 7~11.
The evaluation ＞ of the speed characteristic of ＜ lithium ion batteries
At room temperature, using charge and discharge electrometric determination the device " [TOYO of Battery analyzer Model 1470 " Corporation is manufactured], evaluation electricity pool 1~22 is carried out by following method and compares evaluation with battery 1~11.
On the evaluation of positive pole, 4.2V is respectively charged in from 0.1C and 1.0C electric current, after stopping 10 minutes, with 0.1C and 1.0C electric current is discharged to battery capacity obtained from 2.7V respectively, and speed spy is calculated using following formula Property.
On the evaluation of negative pole, 1.5V is discharged to respectively from 0.1C and 1.0C electric current, after stopping 10 minutes, with 0.1C and 1.0C electric current is discharged to battery capacity obtained from 10mV respectively, and speed characteristic is calculated using following formula (with 0.1C battery capacity and the ratio with 1.0C battery capacity).Mean that the value of speed characteristic is bigger, the reduction of capacity It is fewer, there is good battery behavior., therefore, will be in this evaluation in addition, speed characteristic also relies on the thickness of electrode With 0.1C battery capacity and to be multiplied by the correction factor [0.5 × (thickness (μm) of electrode in the ratio of 1.0C battery capacity )1.4] obtained value is as speed characteristic so that it can be also compared even if the different electrode of thickness.
(speed characteristic [%])=[charging (or electric discharge) capacity under 1.0C] ÷ [hold by the charging (or electric discharge) under 0.1C Amount] × 100 × 0.5 × (thickness (μm) of electrode)1.4
For the lithium ion battery electrode that each embodiment is related to, it is known that：Even in the feelings for thickening the thickness of electrode Under condition, the good lithium ion battery electrode of electronic conductivity can be also formed, although the thickness of electrode is thicker, can also be carried The discharge capacity of the Unit Weight of high active substance.It can act as the good lithium ion battery electricity consumption of the discharge capacity of unit area Pole.
Industrial applicibility
The lithium ion battery electrode obtained by the present invention, it particularly can act as mobile phone, notebook computer and mix Close power vehicle, bipolar secondary battery used for electric vehicle with and lithium rechargeable battery with etc. in the electrode that uses.

Claims (18)

1. a kind of lithium ion battery electrode, it includes：It is configured at the 1st interarea of the barrier film side of lithium ion battery, and configuration The 2nd interarea in current collection side, wherein,
The thickness of the electrode is 50~5000 μm,
Between the 1st interarea and the 2nd interarea, comprising：
Average fiber length is 50nm less than 100 μm of chopped fiber (A),
Average fiber length be more than 100 μm and be less than 1000 μm long fibre (B), and
Active material particle (C),
The chopped fiber (A) and the long fibre (B) are conducting fibre.
2. lithium ion battery electrode according to claim 1, wherein, the chopped fiber (A) is conducting fibre, its Discretely exist between 1st interarea and the 2nd interarea,
The electrical conductivity of the chopped fiber (A) is more than 50mS/cm.
3. lithium ion battery electrode according to claim 1 or 2, wherein, the avarage fiber diameter of the chopped fiber (A) For 0.01~20 μm.
4. according to lithium ion battery electrode according to any one of claims 1 to 3, wherein, the long fibre (B) is conductive Property fiber, it discretely exists between the 1st interarea and the 2nd interarea,
The electrical conductivity of the long fibre (B) is more than 50mS/cm.
5. according to lithium ion battery electrode according to any one of claims 1 to 4, wherein, long fibre (B's) is averaged Fibre diameter is 0.1~100 μm.
6. according to lithium ion battery electrode according to any one of claims 1 to 5, wherein, using the volume of the electrode as Benchmark, the volume ratio shared by the chopped fiber (A) are 0.1~15vol%, and the volume ratio shared by the long fibre (B) is 0.001~15vol%.
7. according to lithium ion battery electrode according to any one of claims 1 to 6, wherein, shared by the chopped fiber (A) Volume (VA) with the long fibre (B) shared by volume (VB) ratio (VA/VB) it is 0.2~50.
8. according to lithium ion battery electrode according to any one of claims 1 to 7, wherein, using the volume of the electrode as Benchmark, the volume ratio shared by the active material particle (C) are 30~80vol%.
9. according to lithium ion battery electrode according to any one of claims 1 to 8, wherein, the active material particle (C) The cladding active material formed at least a portion on surface by the covering cladding containing cladding resin and conductive auxiliary agent Particle.
10. a kind of lithium ion battery, wherein, lithium ion battery according to any one of claims 1 to 9 is used as bearing with electrode Pole and/or positive pole.
11. a kind of manufacture method of lithium ion battery electrode, it is lithium-ion electric according to any one of claims 1 to 9 The manufacture method of pond electrode, it includes：
Process (Q1), the slurry of the chopped fiber (A), the long fibre (B) and the active material particle (C) will be included (Y) it is coated on film (E)；And
Process (Q2), is pressurizeed or is depressurized, and makes the active material particle (C), the chopped fiber (A) and the long fibre (B) it is fixed on the film (E).
12. the manufacture method of lithium ion battery electrode according to claim 11, wherein,
The slurry (Y) is the electrolyte paste (Y1) containing electrolyte (D)；
The film (E) is passes through the electrolyte (D), but the film for passing through the active material particle (C)；
In the process (Q2), pressurizeed or depressurized, the electrolyte (D) is removed through the film (E).
13. the manufacture method of the lithium ion battery electrode according to claim 11 or 12, wherein, at the process (Q2) Afterwards, the suppression process (Q3) to be pressurizeed with stronger pressure to slurry (Y) is carried out.
14. the manufacture method of the lithium ion battery electrode according to any one of claim 11~13, wherein, the film (E) electrical conductivity is more than 100mS/cm.
15. the manufacture method of the lithium ion battery electrode according to any one of claim 11~14, wherein,
Enter the lithium ion battery for being about to be fixed on the film (E) to be transferred to electrode on the interarea of collector or barrier film Process (Q4), the lithium ion battery being arranged at so as to form lithium ion battery with the 1st interarea of electrode on the interarea of barrier film are used Electrode, or, form the lithium ion battery electricity consumption that lithium ion battery is arranged at the 2nd interarea of electrode on the interarea of collector Pole.
16. a kind of manufacture method of lithium ion battery electrode, it is the lithium ion described in any one in claim 1~9 The manufacture method of electrode for cell, its spy include：
Process (T1), the slurry of the chopped fiber (A), the long fibre (B) and the active material particle (C) will be included (Y) coating on the current collector, forms pulp layer on the current collector；And
Process (T2), barrier film is placed on the pulp layer, imbibition is carried out from the upper surface side of barrier film, so that the activity Material particle (C), the chopped fiber (A) and the long fibre (B) are fixed between the collector and the barrier film.
17. the manufacture method of lithium ion battery electrode according to claim 16, wherein, the slurry (Y) be containing The electrolyte paste (Y1) of electrolyte (D).
18. the manufacture method of the lithium ion battery electrode according to claim 16 or 17, wherein, in the upper of the barrier film Liquid absorbent material is placed on surface, and imbibition is carried out from the upper surface side of the barrier film.
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